Effects of the initial nitridation of a sapphire(0001) substrate and the thickness of a low-temperature GaN buffer layer on the polarity of GaN{0001} films grown by rf plasma-assisted molecular beam epitaxy (MBE) have been investigated by coaxial impact collision ion scattering spectroscopy (CAICISS). The volume ratios of each domain in grown GaN{0001} films, that is, (0001) and (0001), were evaluated by making comparisons between the experimental results of the incident angle dependences of Ga and N signal intensities and simulated ones. It was determined that the initial nitridation of a sapphire(0001) substrate increases the volume ratio of the (0001) domain in the grown film and, on the contrary, a thick low-temperature GaN buffer layer increases that of the (0001) domain.